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A room temperature procedure for the partial extraction of heavy metals from soils was investigated in order to find an optimum combination of acid type, acid strength and digestion period. Hydrochloric and nitric acids were compared. The optimum set of variables would produce a maximum amount of adsorbed metal extraction, with a minimum amount of damage to the soil crystal structures, in the shortest possible time span. Samples were analyzed for aluminum, iron, lead, manganese and zinc. In addition, the amounts of metals extracted by the room temperature procedure were compared with the amounts of metals obtained from both a total extraction and a partial extraction procedure involving heat. The chosen optimum combination technique was performed on a known metals trend area. No clearly optimal combination of acid strength and digestion time was found which would be applicable to varying types of soils; statistical analysis yielded a compromise point of 1.4N hydrochloric acid and 10.5 hour digestion period, as the most suitable combination. This combination of variables proved suitable since predicted results were obtained from the known metals trend area. Nitric acid was eliminated due to the acid’s lower reactivity. Room temperature extractions using strong acids at extended contact times were found to attack silicate minerals, but solutions stronger than have previously been used may be utilized without damage to the soil structure. Extractions utilizing heat and concentrated acids were too destructive to be considered true partial extractions. / M.S.

Thesis (PhD (Botany and Zoology)) -- University of Stellenbosch, 2006. / Metals are natural elements of the earth crust usually present at low concentrations in all soils. Although many metals such as cobalt, copper, iron and zinc are essential to living organisms, at elevated concentrations most metals are toxic to organisms living in and on soils. Elevated concentrations of metals are caused either by anthropogenic deposition following remobilisation from the earth crust or are of natural origin. Ultramafic soils do not only pose unfavourable living conditions such as drought and poor organic content, these soils are also characterized by extremely high concentrations of a range of metals known to be toxic under normal circumstances. Ultramafic soils are of high ecological importance as a high proportion of endemic organisms, especially plants, live on these soils. As it is known that earthworms do occur in ultramafic soils, the aims of the present study were to investigate the abilities of earthworms to survive in these soils and the influences of elevated chromium, cobalt, copper, manganese and nickel levels. For the evaluation of the metal background conditions, soils originating from ultramafic rocks of the Barberton Greenstone Belt, Mpumalanga, South Africa were collected and different fractions representing different levels of bioavailability were analyzed for arsenic, chromium, cobalt, copper, manganese and nickel. To assess the mobile, readily available metal fraction, i.e. Ca2+- exchangeable metal cations, a 0.01 mol/L CaCl2 extraction was performed. To investigate the mobilisable metal fraction, representing the amount of easily remobilisable complexed and carbonated metal ions, a DTPA (di-ethylene-triamine-pentaacetic acid) extraction was conducted. In relation to non-ultramafic or anthropogenic contaminated soils, a far lower proportion of metals were extractable by the above mentioned extraction methods. To investigate the availability and effects of these metals on earthworms, two ecophysiologically different species were employed. Aporrectodea caliginosa and Eisenia fetida were long-term exposed to the ultramafic soils collected at the Barberton region and a control soil from a location at Stellenbosch with a known history of no anthropogenic metal contamination. The responses to the ecological stress originating in the ultramafic soils were measured on different levels of earthworm organisation. As endpoints affecting population development, cocoon production, fecundity and viability were evaluated. On individual level, growth, metal body burden and tissue distribution were investigated. As endpoints on subcellular level, the membrane integrity was assessed by the neutral red retention assay, the mitochondrial activity was measured by the MTT colorimetric assay and as a biomarker for the DNA integrity, the comet assay was performed. Focussing on manganese and nickel, the uptake by E. fetida of these metals was investigated with the exclusion of soil related properties using an artificial aqueous medium to draw comparisons to the uptake of these metals in natural soils. The possible development of resistance towards nickel was tested by exposing pre-exposed (for more than 10 generations) E. fetida specimens to ultramafic soils with concentrations of more than 4000 mg/kg nickel. The results showed that, except on the endpoint survival, which was less sensitive than all other bioassays, significant responses to the ultramafic challenge were observed in all earthworm bioassays and on all levels of organisation. The sensitivity of the responses of the earthworms towards the ultramafic conditions was not predictable by the level of organisation. The two species showed different strategies of metal elimination. In A. caliginosa, metals such as nickel, manganese and chromium were transported to the posterior section and the posterior section was subsequently pushed off by autotomization. In E. fetida, metals such as chromium and nickel were sequestered in storage compartments in the coelomic cells or fluid. Other metals, such as cobalt, were not taken up at elevated concentrations. Although an increased accumulation of nickel was observed in E. fetida specimens pre-exposed to nickel, development of resistance or cross resistance was not observed in this species. In contrast, pre-exposed specimen exposed to elevated concentrations of nickel showed a higher sensitivity in terms of survival, indicating the absence of acclimatisation or even genetic adaptation. A comparison of the two species employed indicated that A. caliginosa was less suited for the assessment of the ultramafic soils due to the high individual variation in metal body burden, the mass loss observed and the slow reproduction rate even in the control soils. This happened despite the fact that A. caliginosa was a soil dwelling species supposed to be better adapted to the soil substrate than the litter dwelling E. fetida. The toxicity of the ultramafic soils was not necessarily related to total or environmentally available amounts of the selected metals. Thus, it can be speculated that either these soils contained unidentified toxicants with resulting interactions between toxicants playing an important role or earthworms were able to remobilize metals occurring in these soils. As the singular application of an ecotoxicological endpoint did not give reliable results, especially seen over the duration of the exposures, it can be concluded that, when studying soils with such a complex composition, the utilisation of endpoints addressing different levels of organisation is necessary for the assessment of toxic stress emerging from these ultramafic soils.

Thesis (MTech (Chemistry))--Cape Peninsula University of Technology, 2016. / Polycyclic aromatic hydrocarbons (PAHs) are an alarming group of organic substances for humans and environmental organisms due to their ubiquitous presence, toxicity, and carcinogenicity. They are semi-volatile substances which result from the fusion of carbon and hydrogen atoms and constitute a large group of compounds containing two to several aromatic rings in their molecule. Natural processes and several anthropogenic activities involving complete or incomplete combustion of organic substances such as coal, fossil fuel, tobacco and other thermal processes, generally result in the release of the PAHs into the environment. However, the fate of the PAHs is of great environmental concern due to their tendency to accumulate and their persistence in different environmental matrices and their toxicity. Animal studies have revealed that an excessive exposure to PAHs can be harmful. Evidence of their carcinogenic, mutagenic, and immune-suppressive effects has been reported in the literature. In the soil environment, they have the tendency to be absorbed by plants grown on soil being contaminated by the PAHs. It is, therefore, important to evaluate their occurrence levels in different environmental matrices such as soil concentrations.

This study evaluated the efficacy of bioremediation as a treatment option for a hydrocarbon and heavy metal contaminated soil. Microbial degradation of hydrocarbons under aerobic, nitrate-reducing and sulphate-reducing conditions was examined. Nutrient supplementation with nitrogen and phosphate as well as aeration seemed to be the most important factors for enhancing biodegradation. From initial batch studies, a carbon: nitrogen ratio of 50: 1 was found to be optimal for biodegradation. However, very low carbon to nitrogen ratios were undesirable since these inhibited microbial activity. Manipulation of the pH did not seem to be beneficial with regard to hydrocarbon biodegradation. However, low pH values induced elevated concentrations of leachate heavy metals. Aerobic conditions provided optimal conditions for hydrocarbon catabolism with up to 54% of the original contaminant degraded after 2 months of treatment. Further treatment for up to 20 months did not significantly increase hydrocarbon biodegradation. Under nitrate- and sulphatereducing conditions, 6% and 31 % respectively of the initial contaminant was degraded after 2 months while after a further 20 months, 50% and 42%, respectively were degraded. The addition of soil bulking agents and the use of sparging did not significantly increase biodegradation. Similarly, the addition of inoculum did not influence biodegradation rates to any great degree. The presence of heavy metals up to concentrations of 400 mgt1 Mn, 176 mgt1 Zn and 94 mgt1 Ni did not reduce microbial activity within the soil. During the treatment phase, heavy metal and hydrocarbon migration were limited even under water saturation and low pH conditions. A Biodegradation Index was developed and evaluated and may, potentially, find use as an in situ assessment technique for microbial hydrocarbon catabolism. The iodonitrophenyltetrazolium salt assay was also found to be an effective and rapid alternative assay for monitoring bioremediation progress. / Thesis (M.Sc.)-University of Natal, Pietermaritzburg, 1996.

The emission of trace metals (TMs) into boreal forest regions of the northern hemisphere is an important environmental issue due to their potential detrimental impacts on these sensitive ecosystems. One of the foremost factors controlling metal cycling is the chemistry of the overlying organic forest floor of the forest soil. In this thesis we examine the chemistry of forest floor horizons of podzolic soils. Our goal is to improve our ability to predict the partitioning of metals between the soil solid and solution phases. / We developed a standard protocol to produce solutions that resemble lysimeter solutions from podzolic soils using air-dried samples. We hypothesized that the stabilization point of the electrical conductivity (EC) of the soil solution is indicative of the point in which soluble salts and organic material precipitated during sampling and storage are removed from the soil particle surfaces. Solutions produced by leaching the soils, once the EC of wash solutions had stabilized, were comparable to lysimeter solutions from the area where samples were collected with respect to the concentrations of divalent cations, pH, EC and dissolved organic carbon (DOC). The applicability of this procedure to trace metal partitioning in forest floors was explored. Laboratory extractions produced partition coefficients (log Kd) similar to observed lysimeter solutions ranging from 3.4 to 3.9 for Cd, 3.4 to 3.9 for Cu, 3.4 to 4.1 for Ni, 4.1 to 5.2 for Pb and 3.2 to 3.5 for Zn. According to a semi-mechanistic regression model based on observed lysimeter concentrations, the metal concentrations in solution were appropriate relative to known factors that influence metal partitioning in soils: pH, the concentrations of total metals and DOC. / While chemical characteristics of soils have been consistently observed to play important roles in the partitioning and toxicity of metals we wished to place the importance of the chemical characteristics of soil on mobility and toxicity in context. We interpreted field data that had been collected from transects established with distance from two point source emitters in Rouyn PQ, and Sudbury ON. Canada find developed equations that predict dissolved metal concentrations from total metal concentrations, soil pH, soil organic matter (SOM), and DOC contents. We integrated these equations into a simple box model that calculates changes in the concentration of metals in the organic and upper mineral horizons and includes a loop for vegetative return of metals to the forest floor.

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by Lau Wai Man. / Thesis (M.Phil.)--Chinese University of Hong Kong, 1981. / Bibliography: leaves 189-205.

Thesis (MSc. Agriculture (Soil Science)) -- University of Limpopo, 2019 / Global shortage of fresh quality water has led to the use of treated wastewater in arid and semi-arid regions. Although, the treated wastewater has proven to be the best solution in ameliorating pressures brought by water shortage, it contains toxic heavy metals, some in high concentrations that could possibly pose health risks and degrade soil quality. Therefore, the objectives of the study were to determine the vertical and horizontal distribution of bioavailable heavy metals on virgin, cultivated and fallowed fields and to investigate the bioremediation abilities of selected soil microbes on non-essential heavy metals in cultivated and fallowed soils following irrigation with treated wastewater at University of Limpopo (UL) Experimental Farm. Three fields, namely, virgin field (VF), cultivated field (CF) and fallowed field (FF), each being 6.4 ha, were each divided into 40 equal grids, equivalent to 40 m × 40 m, which were used in vertical assessment of heavy metals. Soil profiles were established inside each grid and soil samples collected at 0-20; 20-40 and 40-60 cm soil depth for further laboratory analysis. The soil samples were analyzed for basic soil physico-chemicals, namely, particle size distribution, soil pH (H20 and KCl), electrical conductivity (EC), reduction potential (Eh), organic carbon (OC) and cation exchange capacity (CEC). Five essential heavy metals namely zinc (Zn), iron (Fe), copper (Cu), cobalt (Co), manganese (Mn) and five non-essential heavy metals, namely, arsenic (As), chromium (Cr), lead (Pb), aluminium (Al), and cadmium (Cd), were also extracted from the soil samples. Heavy metal resistant Gram-negative (–) and Gram-positive (+) bacteria were isolated from the soil and identified as Providencia rettgeri (–), Enterobacter cloacae (–), Bacillus cereus (+) and Arthrobacter aurescens (+). xix The isolated bacteria were cultured and inoculated in heavy metal-contaminated soils and incubated for 12 weeks to bioremediate the non-essential heavy metals. Results obtained suggested that the treatments had no significant (P ≤ 0.05) effects on vertical distribution of all the essential and non-essential heavy metals among the three fields. However, on average Co was above the permissible level at 53 mg/kg in CF at 0-20 cm and although all the other essential heavy metals increased, they were still within the permissible levels. The concentration of As was also above the permissible levels in CF with an average concentration of 4.30 mg/kg. Cadmium levels were also above the permissible levels in CF with an average concentration of 1.146 mg/kg in CF and this increased by 0.46 units from VF which had an average value of 1 mg/kg. However, fallowing reduced Cd to 0.51 mg/kg which was below or within the expected limits in soil previously irrigated with treated waste water. Gram-positive bacteria reduced more concentrations of non-essential heavy metals separately and combined, especially in the fallowed field. Irrigation with treated wastewater has shown to have both negative and positive effects on the concentration of essential and non-essential heavy metals in cultivated and fallowed fields. Bioremediation coupled with fallowing has been proven to be the best solution in ameliorating heavy metal toxicity while naturally improving the quality of the soil. / National Research Foundation (NRF)